TY - JOUR
T1 - Copolymerization Approach to Improving Ru(II)-Complex/C3N4 Hybrid Photocatalysts for Visible-Light CO2 Reduction
AU - Tsounis, Constantine
AU - Kuriki, Ryo
AU - Shibata, Kengo
AU - Vequizo, Junie Jhon M.
AU - Lu, Daling
AU - Yamakata, Akira
AU - Ishitani, Osamu
AU - Amal, Rose
AU - Maeda, Kazuhiko
N1 - Funding Information:
This work was supported by a Grant-in-Aid for Young Scientists (A) (Project JP16H06130) from JSPS. It was also partially supported by a Grant-in-Aid for Scientific Research on Innovative Area “Mixed Anion (Project JP16H06441, JP16K21724 and JP17H05489)” and a CREST program (Project JPMJCR13L1) (JST). R.K. acknowledges support by a JSPS Fellowship for Young Scientists (JP17J03705). C.T. acknowledges support by the Australian Research Council (ARC) under the Laureate Fellowship Scheme FL140100081, and Tokyo Tech Winter Program.
Publisher Copyright:
© 2018 American Chemical Society.
PY - 2018/11/5
Y1 - 2018/11/5
N2 - Copolymerized carbon nitride nanosheets (NS-C3N4) were used as a light absorbing unit while paired with a Ru(II) complex that served as a catalyst for CO2 reduction, forming a hybrid photocatalytic system. Copolymerization with urea and phenylurea in air at 823 K resulted in a carbon nitride material that had wide visible light absorption extending to 650 nm, significantly red-shifted compared to the absorption edge of pristine NS-C3N4, an analogue prepared with only urea (ca. 435 nm). While a hybrid system consisting of pristine NS-C3N4 was found to be inactive under longer wavelength visible light (λ > 500 nm) due to its large band gap, the copolymerized material was able to catalytically convert CO2 to HCOOH under λ > 500 nm irradiation. Furthermore, its activity toward HCOOH production is doubled under λ > 400 nm irradiation after 5 h compared to pristine NS-C3N4. Transient absorption spectroscopy clearly showed improved lifetime of photogenerated free (and/or shallowly trapped) electrons, which should be the key to enhancing the photocatalytic activity of this hybrid system even under shorter wavelength visible light.
AB - Copolymerized carbon nitride nanosheets (NS-C3N4) were used as a light absorbing unit while paired with a Ru(II) complex that served as a catalyst for CO2 reduction, forming a hybrid photocatalytic system. Copolymerization with urea and phenylurea in air at 823 K resulted in a carbon nitride material that had wide visible light absorption extending to 650 nm, significantly red-shifted compared to the absorption edge of pristine NS-C3N4, an analogue prepared with only urea (ca. 435 nm). While a hybrid system consisting of pristine NS-C3N4 was found to be inactive under longer wavelength visible light (λ > 500 nm) due to its large band gap, the copolymerized material was able to catalytically convert CO2 to HCOOH under λ > 500 nm irradiation. Furthermore, its activity toward HCOOH production is doubled under λ > 400 nm irradiation after 5 h compared to pristine NS-C3N4. Transient absorption spectroscopy clearly showed improved lifetime of photogenerated free (and/or shallowly trapped) electrons, which should be the key to enhancing the photocatalytic activity of this hybrid system even under shorter wavelength visible light.
KW - Artificial photosynthesis
KW - Carbon nitride
KW - Heterogeneous photocatalysis
KW - Hybrid photocatalyst
KW - Solar fuels
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U2 - 10.1021/acssuschemeng.8b03782
DO - 10.1021/acssuschemeng.8b03782
M3 - Article
AN - SCOPUS:85056264731
SN - 2168-0485
VL - 6
SP - 15333
EP - 15340
JO - ACS Sustainable Chemistry and Engineering
JF - ACS Sustainable Chemistry and Engineering
IS - 11
ER -
